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Marine Permian of western Europe: beautiful rocks, remarkable stories Maurice Tucker Bristol 20 APRIL 2016 Marsden, NE England THE ZECHSTEIN: TALK OUTLINE Zechstein sequence stratigraphy: some points of view, carbonate-evaporite systems Zechstein reservoirs: oolites, reefal-buildups and microbialites, slope facies, breccias Zechstein source rocks: biomarkers, basin redox using data from outcrop (North East England – North Germany) and the subsurface to discuss stratigraphy, facies, diagenesis, porosity and biomarkers. ZECHSTEINKALK Ca1 (reef) KUPFERSCHIEFER YELLOW SAND / ROTLIEGEND ______________________________ CARBONIFEROUS (COAL MEASURES) Claxheugh Rock, NE England Late Permian 250 Ma P A N G To Panthalassa Ocean * ← LAU R U S S IA→ Stavanger Zechstein Sea ?? E A subduction PALAEO-TETHYS OCEAN LATE PERMIAN PALAEOGEOGRAPHY FROM BLAKELY (2014) Zechstein Sea connected to Panthalassa Ocean 2000 km to north/northeast. GONDWANA Possible connection to Palaeo-Tethys through the Polish Sub-basin to the southeast (??) (Africa) Palaeo-latitude: 10-20o. Climate extremely arid. Permian, Zechstein NE England, Germany, East Greenland. afterUpper Ron Blakey accessed in outcrops: 2012 OPEN OCEAN, 2000 KM NORTH Zechstein palaeogeographic map for the Z2 Main Dolomite (Ca2) Northern Permian Basin Southern Permian Basin POSSIBLE CONNECTION TO PALAEO-TETHYS Wells marked are those used in recent biomarker and facies study (Slowakiewicz, Tucker et al. 2013, 2015, 2016) Zechstein correlation: Southern to Northern Permian Basin ZECHSTEIN STRATIGRAPHY TRADITIONALLY DIVIDED INTO CARBONATE-EVAPORITE CYCLES From TGS website Cycles can be correlated SPB to NPB: facies similar but some differences in thickness, reflecting subsidence / faults. In NPB: more local clastic input, some younger carbonates (Z4). Continuity of strata across the 2 basins – although strong facies and thickness changes, especially in the carbonates and anhydrite. But some useful gamma-ray peaks (Kupferschiefer, Sapropelic Marker). Correlation of well-logs may be hampered by evaporite dissolution and/or halite diapirism. ZECHSTEIN CARBONATE – EVAPORITE CYCLES: Lithostrat for NE England Z5 Z4 Z3 Plattendolomit Ca3 Hauptdolomit Ca2 Ca1b Zechsteinkalk Ca1a Z2 Z1 Marginal carbonate platforms Basinmargin anhydrite and basin-centre halite. Zechstein cycles Z1 (Werra), Z2 (Stassfurt), Z3 (Leine), Z4 (Aller), Z5 (Ohre) APPLICATION OF SEQUENCE STRATIGRAPHY Sequence stratigraphic models for carbonate evaporite Basins (Tucker 1991) Point to note: basin needs to be cut-off from open ocean for evaporites to precipitate. Evaporites also precipitated on platform during TST-HST. 2 models: complete and incomplete drawdown. SCHEME OF TUCKER (1991) FOR NE ENGLAND AND Premise: ADJACENT NORTH SEA ZS7 ZS6 ZS5 ZS4 ZS3 ZS2 ZS1 Figure from Catuneanu et al. (2011). basin-centre evaporites are lowstand (LST); carbonates are TST-HST. Note: 2 sequences in Z1 carbonates, ZS1, ZS2, then 2 evaporitecarbonate sequences ZS3, ZS4, and then 3 evaporite-clastic sequences ZS5, 6, 7. Other schemes, e.g. Strohmenger ‘96, where SB in middle of evaporites, so they are TST-HST / LST. SEQUENCE STRATIGRAPHY TODAY: (see Catuneanu et al. 2011 for review) 4-systems tract model (rather than 3) now regularly applied in sequence stratigraphy: the FSST for sediments deposited during sea-level fall: FALLING STAGE SYSTEMS TRACT. time Not all systems tracts always developed in each sequence, or in all areas of the basin. SB time or SB can be placed below or above FSST – wherever most appropriate. SB SB SB 4-systems tract sequence stratigraphic model showing higher-frequency cycles (parasequences) and sequence boundary above the FSST and below the LST. From Coe et al. (2003) based on Hunt & Tucker (1992). EARLIER SCHEMES HAD 3 SYSTEMS TRACTS, NOW 4 FSST FACIES CAN BE RECOGNISED AT TOP OF EACH CARBONATE PLATFORM: RAISBY (Ca1a), FORD (Ca1b) ROKER (Ca2) and SEAHAM (Ca3) in NE England and elsewhere in SPB. = FSST FSSTs ARE CARBONATES – SO LOGICAL TO PLACE SB ABOVE FSST Sequence stratigraphy still useful ! BASIN-MARGIN AND BASIN-FILL EVAPORITES: The role of evaporites in loading and increased subsidence A shallow-basin model for ‘saline giants’ based on isostasy-driven subsidence. Papers by van den Belt & de Boer (2007, 2014). Zechstein strata consists of: thick basin-margin carbonates, thick basin-margin gypsum wedge or isolated platform, and thick basin-fill salt, with extremely thin basin-floor carbonate or gypsum. However, salt dissolution-diapirism and anhydrite dissolution can complicate matters; plus synsedimentary tectonics. GREAT THICKNESS AND FACIES VARIATIONS: E.G. NORWEGIAN SECTOR. Well 16/4-1 Well 17/4-1: 1180 m A4 Ca4 Z4 evaps: 50 m Very thick Na3 + K: 725 m Ca3+A: 50 m Na3 Thick Na2 salt: 320 m Ca2+A: 7 m Na-Sh Ca1+A: 7 m X X X 25/10-2R Na2 Z4 Z3 X 17/4-1 Ling Graben – 1180 m X 25/10-2 Utsira High – 110 m X 16/4-1 margin Utsira High – 190 m. Logs and data from NPD. Topographic-tectonic control + possible salt dissolution-diapirism. Na3 A3 Ca3 Ca2 RotL Na3 K3 A2 Ca1 Na3 K3 Na2 Ca2 Ca1 Rotl Na/K Na3 ZECHSTEIN RESERVOIRS Different types: oolites (oooo), reefal-buildups (R), slope facies (+ fractures, fffff), and breccias (xxBxx). OOLITES: Ca2 especially, also Ca3; REEFAL-BUILDUPS: Ca1, Ca2; SLOPE FACIES: Ca2 xxBxx R BRECCIAS – different types: evaporite dissolution-karst collapse; limestone karst; reefal debris; resedimented slope facies; tectonic; hydrofractured-hypogene. OOLITE RESERVOIRS: NE YORKSHIRE, THE NETHERLANDS, GERMANY, POLAND PLATFORM-MARGIN GRAINSTONES NE ENGLAND SUBSURFACE – MALTON-4 well, North Yorkshire NPB Mid North Sea High SPB Well log of Malton-4 (21 on map) showing location of oolite units, towards top of likely high-frequency cycles. Parasequences in Ca2 can be recognised quite widely across SPB. Gas reservoir. OOID SHOAL FACIES WITH OOMOLDIC POROSITY. MALTON-4 (4190’, 4183’) δ13C 6.3 ‰, δ18O -2.2 ‰. Leaching profiles revealed in sonic logs from the Z2 carbonate (well Exloo-2), the Netherlands. Clark, 1987. REEFAL-BUILDUP RESERVOIRS Ford Formation, reef, back-reef, fore-reef facies. Bryozoan-microbial reefs with other biota. Much marine cement. BASINAL REEF EQUIVALENT A1 Werra (Hartlepool) Anhydrite 10 cm 10 cm Ford Fm (Ca1b) ----------------------Raisby Fm (Ca1a) Reefal basin facies (Ca1b): The Trow Point Bed: a 10-50 cm bed of microbial laminites and oncoids = 100 metres of reef, which can be traced from NE England to Poland. Zechstein basin floor starved of sediment. CONTINUITY OF ZECHSTEIN STRATA: Ca2 Ca1b Zechsteinkalk ROTLIEGENDE Ca1a Kupferschiefer Argyll 30/24-26: columnar microbialites, equivalent to Trow Point Bed of NE England at top of Ca1 (Zechsteinkalk), which here is 25 cm thick. Thumb-nail for scale. Remarkable continuity of 10 cm thick bed over 1000 km of basin floor, = 100 m reef. POROSITY: INTERCRYSTALLINE FROM REFLUX DOLOMITISATION by seawater / evaporated seawater |---- 1 cm ----| Ford Fm (Ca1b) reef-core facies – mottled vuggy dolomite with suggestion of former colonial organisms in thin-section. δ13C 6.3 ‰, δ18O -1.2 ‰. REEFAL RESERVOIRS (Dyjaczynski, Peryt et al. 2001) Wolsztyn Ridge central Polish Basin Ca1b reef sitting directly on Carboniferous ridge Seismic of Koscian reef area Z1 reef Outline of Bronsko reef complex Z1 reef Best poroperm in reef-core facies REEFAL RESERVOIRS * RECENT DISCOVERIES NORTH SEA Time-slice map flattened on base Zechstein showing the outline of a Z2C isolated carbonate platform on the southern side of the Mid-North Sea High (Jaarsma et al. 2014). East-West seismic cross-section through well E02-02 near the margin of the platform. Isolated buildups controlled by pre-existing Carboniferous topographic highs. TARGET: Buildups and oolite bodies at platform margin. AND FARTHER NORTH… MORE BUILDUPS: NW Europe-Greenland in the Kazanian (255 Ma) from Dore (1992) and Bugge et al (2002). Jameson Land, East Greenland Wegener Halvø Fm = Z1, Z2 (Stemmerik 2001, pers comm 2016) Wegener Halvø Fm: buildups and flank facies with bryozoans, microbes, bivalves, flank facies. Buildups exposed and karstified. Also oolites. Close to basinal source rocks. Scholle et al. SLOPE FACIES RESERVOIRS: cores from offshore NE England and Polish sub-basin Laminites, turbidites, slumps, bioturbated lime mudstones Reservoir controls: porous zones in coarse resedimented units, plus microporosity and fracturing of tight facies, BUT loss of porosity through dedolomitisation. Slope facies are also the source rock. SLOPE FACIES IN THE FIELD Upper slope facies: slumps, channels, debrites Lower slope facies: turbidites, laminites. SLOPE RESERVOIRS Poland Sub-basin Main Dolomite of Grotow (Slovakiewicz & Mikolajewski 2009). Reservoirs in shelf oolite and slope breccias and turbidites. MICRO- NANO- POROSITY IN SLOPE FACIES: Inter-crystal/particle pores in calcite-dominated facies. A) Irregular, embayed to curved crystal boundaries (red arrow) common pores. Note also intra-crystal pores (green arrow); E) Bitumen (dark area in the centre) hosted in a large inter-crystal pore. Slowakiewicz, Perri & Tucker (Jour Petroleum Geology, 2016) MICRO- NANO- POROSITY IN SLOPE FACIES: Above L: Intercrystal pores in laminated dolomite mudstone. Egton High Moor. Depth 1373 m. Above R: Calcite spar with intra-crystal pores, irregular to polyhedral cavities. Depth 3324 m. Right: Intracrystal pores in anhydrite containing bitumen. Well Petrykozy-4K. Depth 2822 m. OIL DROPLETS IN MICROCAVITIES IN SLOPE FACIES Intracrystal pores containing oil / bitumen remnants (spheres). Laminated lime mudstone, slope facies. Poland Well WK-8, depth 3109 m. Slowakiewicz, Perri & Tucker (2016). FRACTURES IN SLOPE FACIES Z2 Slope facies, depth 2590 m. Polish sub-basin. Fractures: some filled, some open, some offset, brecciated zone + vugs. FRACTURES AS LOCATIONS OF BURIAL DISSOLUTION Microporosity developed along fractures; bitumen in stylolites. Subsurface Netherlands, depth 2430 m. FRACTURES VERSUS MATRIX Fracture filled with anhydrite cement, whereas matrix retains its original high intergranular porosity. Fluid flow concentrated in fractures so they are cemented up. Subsurface Netherlands, depth 2450 m. SLOPE FACIES RESERVOIRS: another factor to consider is dedolomitisation Reduced porosity through dedolomitisation calcite v dolomite poroperm From Schoenherr et al. (S&D, 2014) DEDOLOMITISATION DURING MODERATE BURIAL: associated with gypsum dehydration to anhydrite dedolomite distribution In German Sub-basin, Zechstein not uplifted, totally buried to 5 km since deposition. Dedolomites /secondary limestones mainly in Ca2 slope facies, some in platform. Formed through fluids migrating out of evaporites and organic-rich sediments. From Schoenherr et al. (2014). Model for subsurface dedolomitisation: related to gypsum – anhydrite dehydration releasing much water and Ca2+; CO2 from organic matter decomposition also driving the process. LIMESTONE DEDOLOMITE / SECONDARY LIMESTONE AT OUTCROP IN NE ENGLAND DOLOMITE Often close to evaporite units Grey limestone in coarser-grained lenses in upper slope facies. LIMESTONE DOLOMITE Dark-grey to black organic-rich laminated limestone in lower slope facies (= Sapropelic Marker in well logs). Units with thickerturbidites (buff) largely remain as dolomite. SECONDARY LIMESTONE / DEDOLOMITE in Ca2 Roker Fm. NE England: following facies. DOLOMITE δ13C = +6.0 ‰ δ18O = +1.4 ‰ Calcitised slope laminites, Roker Fm., NE England. PPL & XP. δ13C = 5.8 ‰, δ18O = -4.0 ‰. Secondary limestone - dedolomite MODERATE BURIAL: DEDOLOMITISATION-NEOMORPHISM A spectrum from NEOMORPHOSED LIMESTONE THROUGH TO DEDOLOMITE - related to gypsum dehydration releasing Ca2+ ions, water and CO2 from organic matter decomposition. Figure Tucker 2016 HYDROTHERMAL-HYPOGENE BRECCIA RESERVOIRS Lockton-2a, Yorkshire, NE England: a 1970s gas reservoir with many fractures and faults, and mineralisation. Highly-fractured slope facies with dolomite fracture fills. Lockton-2. From an area of extra-high heat-flow and high VRo in vicinity of major tectonic Lineament in the Cleveland Basin. Hydrothermal – deep burial dolomite + bitumen. Scale bar = 1 mm. Lockton-2a: saddle /baroque dolomite. Isotopes: δ13C 4.2 ‰, δ18O -13.95 ‰. ZECHSTEIN BRECCIAS 1) Evaporite dissolution 2) Limestone karst Classification of cave breccias and sediment fills (Loucks et al. 2004). Evaporite collapse breccia: internal stratigraphy (from Gutteridge & Tucker). OFTEN DIFFICULT TO TELL DIFFERENCE BETWEEN THESE BRECCIA TYPES IN CORE CONTEXT IMPORTANT BRECCIAS: 30/24-26 Argyll. Zechstein carbonate (~30 m) thick. Argyll 30/24-26 depth 9158’ and 9165’. Collapse breccia likely from dissolution of A1. Note differences in amount of matrix and some streaked out clasts. Variable matrix. MAJOR OIL RESERVOIR (actually first in North Sea) BRECCIAS: 14/19-C41 (Claymore) – Zechstein carbonate (35 m thick) LEFT: Breccia with reddish colour, some laminated internal sediment, calcite spar-filled cavities. Probably palaeokarstic (limestone dissolution) breccia, top of Ca2, depth 10324’. RIGHT: Higher up, clay-matrix breccia = collapsed brecciated Ca3 after dissolution of A2 evaps. Claymore area was a structural high in the basin, but not so deep. PALAEOKARST BRECCIA Palaeokarstic surface with reworked breccia of limestone clasts within Zechsteinkalk, between Ca1a (ZS1) and Ca1b (ZS2) at Zechstein sequence boundary 2 (ZSB2) (Seesen, Harz, Germany, last week). COLLAPSE BRECCIA FROM DISSOLUTION OF A1 (WERRA ANHYDRITE) Collapse brecciated Ca2 (Hauptdolomit, Roker Fm) 15 m thick, stratiform breccia. 5 cm residue = 150 m anhydrite A1, 5 km offshore, east. 10 cm Ca1b basin facies = 100 m reef 5 km to west. Ca1a = Raisby Fm. Zechsteinkalk EVAPORITE DISSOLUTION-COLLAPSE BRECCIATION, and DEDOLOMITISATION DOLOMITE COLLAPSE BRECCIA PIPE 1 DEDOLOMITISED COLLAPSE BRECCIA COLLAPSE BRECCIA PIPE 2 DOLOMITE DEDOLOMITISED COLLAPSE BRECCIA Hartlepool Anhydrite (A1) residue 25 m below beach. 2 types of collapse breccia a) stratiform (dedolomitised), b) pipes, later. COLLAPSE BRECCIA Clast of collapse breccia (dedolomitised) which is coated, within a collapse breccia. Dissolved out clasts originally dolomite. Tynemouth, NE England. Slab 15 cm across. EVAPORITE COLLAPSE BRECCIA with laminated sediment, deposited in a cavern in dissolving anhydrite. Residue (10 cm clay) of 150 m anhydrite (A1, Werra). Top surface of basinal Ca1b facies (10 cm thick microbialite = 100 m reef 5 km to west) BEDDED SEDIMENT WITHIN COLLAPSE BRECCIA ABOVE: Laminated sediment, graded laminae, synsed fault, small collapse feature. RIGHT: Laminated sediment with clast of breccia, deposited within cavern in collapsing carbonate, cut by vertical sediment dyke. Clasts dissolved out were dolomite clasts. NE England. Gypsum-anhydrite dissolution and formation of collapse breccias Haupt dolomit Werra Anhydrite Scharzfeld, Harzgebirge. Werra Anhydrite, dissolution surface with Hauptdolomit (Ca2) above. Gypsum-anhydrite dissolution and formation of collapse breccias Collapse Brecciated Ca2 Blocks of brown collapse brecciated Ca2 (Rauchwacke) forming scree. Collapse brecciated Ca2 (Rauchwacke), Walkenried Monastery, Harzgebirge, Germany High TOC in lagoonal microbialites ZECHSTEIN SOURCE ROCKS TOCs & BIOMARKERS High TOC (up to 2%) in lower slope biolaminites, e.g. Ca2 ‘Stink Dolomite’. 3rd CARBONATE PLATFORM Depositional model for Roker Fm (Slovakiewicz, Tucker, Perri, Mawson AAPG Bull 2013) ZECHSTEIN HYDROCARBONS SOURCE ROCKS: Gas from Coal Measures (Carboniferous), Oil from Jurassic, even Devonian, but also Zechstein itself: so Zechstein self-sourcing. Purple sulphur bacteria Archaea BIOMARKERS INDICATIVE OF MICROBES Green sulphur bacteria Green sulphur bacteria isorenieratane Purple sulphur bacteria okenane isorenieratane squalane biphytane okenane ß-isorenieratane ß-isorenieratane chlorobactane Archaea squalane Eukaryotes (esp algae) biphytane PMI sterane chlorobactane PMI Anaerobic bacteria Cyanobacteria Anaerobic bacteria lycopane Cyanobacteria 2-methylhopanes lycopane 2-methylhopanes Terrestrial organic matter indicated by certain hopanes and tricyclic terpanoids INTERTIDAL-SABKHA MICROBIAL FACIES Ph Halophilic archaea and cyanobacteria Intensity Squalene Pr/Ph ratio (0.4) indicates anoxic conditions Offshore Borehole 1 depth 1049ft (319.7 m) Hartlepool Anhydrite (Z1A) biomarkers indicate hypersaline environment and extremophiles (archaea). Squalane Hopanes Pr C26 Time EVIDENCE OF A TERRESTRIAL PLANT CONTRIBUTION Malton-4 4130 ft m/z 191 Malton-4 - western margin of the Zechstein Basin in Yorkshire, lagoonal – microbial facies. Biomarkers: tricyclic C23 and tetracyclic terpanes C24 (and ratio C23/C24) indicate contribution from terrestrial plant material. Hopanes indicate cyanobacteria. Fossil plants occur in Roker Fm. shallow-water facies at outcrop. SLOPE BIOLAMINITE FACIES Hopanes & 2-methylhopanes H Roker Fm, NE England slope biolaminites. Well VT11, depth 312 m C30αβ H m/z 191 H C31αβ C29αβ H H H S R C32αβ C29Ts Intensity Tm BNH? Ts C30αβ m/z 191 C30βα C29βα C31βα S C29Ts S R C33αβ C34αβ S R S 35 R G C32αβ S C30βα C31βα C322αβ m/z 205.1 Time C31βα R R S C31αβ C29αβ C29βα G Biomarkers indicate cyanobacteria. C αβ TOC 2% C33αβ S R R EVIDENCE OF EUXINIA Isorenieratane and its derivatives m/z 133+134 Błotno-3 (3348.15 m) Toe-of-slope apron Poland – eastern SPB Occurrence of chlorobactane and isorenieratane, produced by green sulphur bacteria suggests euxinic conditions in the photic zone (PZE) EVIDENCE OF EUXINIA Slope facies Poland Well WK-8 Slowakiewicz, Perri & Tucker 2016 Native sulphur microcrystals Microcrystals of framboidal pyrite Sulphate reducing bacteria: SO42-+ OM HS- + H2S + HCO3but green sulphur bacteria (anaerobic and photosynthetic) also involved in precipitation of pyrite and sulphur: H2S + CO2 CH2O + H2O + 2S FeS + H2S FeS2 + H2 Model for Polish Sub-basin Depositional models for Zechstein source rocks: formed within anoxic lagoons and where photic zone euxinia developed above slope, mostly in eastern part of basin. Slowakiewicz, Tucker et al. (2013; 2015). Model for Anglo-Dutch sub-basin oxic water column from freshwater river input and Boreal Sea, near-normal salinity OPEN OCEAN, 2000 KM NORTH stratified water column, photic zone euxinia, suboxic bottom water, hypersaline lagoon and tidal flat waters, upwelling, northeasterly and SSW trade winds deep basin, oxic-suboxic water column, from freshwater river input and restricted Boreal Sea, normal-meso salinity anoxic bottom water likely high salinity POSSIBLE CONNECTION TO PALAEO-TETHYS Stable isotopes (C and O) support variations in organic productivity, circulation and redox. Source rocks formed in restricted lagoons and in slope facies where PZE above. CONCLUSIONS The 4-systems tract sequence stratigraphic model with SB after FSST fits the data well. Basin-wide evaporites are all lowstand facies and their deposition involves a disconnect from the open ocean; their successions may have their own internal sub-sequence stratigraphy. Whole range of reservoir types but presence of fractures significant. Breccia is a common reservoir type but often difficult to be sure of origin from core material. Biomarkers indicate variations across the basin in terms of redox; best potential source rocks in the slope and restricted lagoon facies. Fieldwork, Los Roques, Venezuela, January 2006 And finally Why study limestones? because they are 1) interesting, exciting stories, 2) pretty, 3) found in pleasant places and 4) important – they contain more than half the World’s oil. LONG LIVE LIMESTONES Pleistocene, Rottnest Island, W Australia THANK YOU A convenient stop in the desert during fieldwork in Qatar